Application of thin crystalline Si3 N4 liners in shallow trench isolation (STI) structures

ABSTRACT

Silicon integrated circuits use a crystalline layer of silicon nitride (Si 3  N 4 ) in shallow trench isolation (STI) structures as an O 2  -barrier film. The crystalline Si 3  N 4  lowers the density of electron traps as compared with as-deposited, amorphous Si 3  N 4 . Further, a larger range of low-pressure chemical-vapor deposited (LPCVD) Si 3  N 4  films can be deposited, providing a larger processing window for thickness controllability. An LPCVD-Si 3  N 4  film is deposited at temperatures of 720° C. to 780° C. The deposited film is in an amorphous state. Subsequently, a high-temperatures rapid-thermal anneal in pure nitrogen or ammonia is conducted at 1050° C. to 1100° for 60 seconds.

This is divisional of application Ser. No. 08/531,844 filed Sep. 21, 1995.

FIELD OF THE INVENTION

The present invention generally relates to the manufacture of submicron integrated circuits and, more particularly, to the application of thin silicon nitride (Si₃ N₄) films in shallow trench (STI) structures as O₂ -barrier films.

BACKGROUND DESCRIPTION

One of the most critical parameters affecting silicon integrated circuit functionality and yield is the amount of stress that is developed within the silicon substrate during device processing. Stresses, exceeding the mechanical yield strength of silicon (Si), will form Si crystal defects (e.g., dislocations and stacking faults), adversely affecting device performance and yield. A prominent source of stress occurs during the isolation process of electrical devices. Shallow trench isolation (STI) is used for features designed a 0.5 μm or less. This process includes

etching a "shallow" trench (i.e., 0.5 μm or less),

growing a thin oxide immediately after etch,

filling the trench with a dielectric (i.e., deposited oxide),

"densifying" the dielectric, either by oxidizing the dielectric or using a high-temperature anneal in an inert ambient, and

planarization of the dielectric.

As device geometries continue to shrink in size, and since stress is inversely proportional to area, it is of paramount importance to minimize stress during isolation processes as much as possible.

A 256 megabyte (MB) dynamic random access memory (DRAM) chip uses a "deep" trench array (as the capacitors) and STI to isolate the various transistors within the capacitor array. It has been determined that limiting the amount of oxide grown in the substrate is necessary to eliminate Si crystal defects in the trench-capacitor array. The method currently employed to "block-out" oxygen (O₂) in the Si substrate is the use of a thin (<5 nm) silicon nitride (Si₃ N₄) film deposited by low-pressure chemical-vapor deposition (LPCVD) immediately after a thin oxide is grown in the STI. The thickness of the Si₃ N₄ film is specified as being 5 nm or less. The reason for this thickness limitation is that this film has been found to be etch-resistant in hot phosphoric acid baths (e.g., to remove pad Si₃ N₄) as well as in hydrofluoric acid baths (to remove thermally grown oxides). Thicker LPCVD-Si₃ N₄ films used as Si₃ N₄ liners in STI trenches have shown to etch readily in hot phosphoric acids.

One problem associated with the thin Si₃ N₄ liner has been its propensity to trap electrical charge. The charge-trapping behavior (interface and bulk) of the Si₃ N₄ liner has been observed to enhance STI-bounding leakage (N well to N well) in the sense amplifiers (i.e., "support circuitry") of the DRAMs, thus causing high standby currents. Recent data clearly shows that the Si3N4 liner lowers the threshold voltages (Vt) and enhances junction leakage by several orders of magnitude.

To ascertain the amount of charge that is trapped by the Si₃ N₄ liner, blanket wafer experimental lots were processed consisting of (1) thermally-grown oxide (SiO₂ -10 nm), (2) LPCVD-Si₃ N₄ (4 nm), and (3) 10 nm SiO₂ /4 nm LPCVD-Si₃ N₄. Simple metal-insulator-semiconductor (MIS) structures were fabricated by depositing aluminum through a dot mask onto the insulating film(s). C--V measurements (low- and high-frequency) were conducted and result indicated that (1) the thin Si3N4 film alone contains approximately two orders of magnitude more charge-trapping states than the oxide (i.e., 10¹² versus 10¹⁰), and (2) the combination of the oxide and Si₃ N₄ decreases the density of charge-trapping states only marginally (e.g., ˜5×10¹¹ versus 10¹⁰). Ideally, it would be best to develop or deposit a thin Si₃ N₄ film that would not trap charge and still be resistant to hot phosphoric acid and hydrofluoric acid.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a thin Si₃ N₄ film which has a lower density of trapping centers than as-deposited LPCVD-Si₃ N₄ and is an extremely effective as an O₂ -barrier film yet is resistant to hot phosphoric acid and hydrofluoric acid.

According to the invention, thin crystalline Si₃ N₄ films are applied in STI structures as O₂ -barrier films. The crystalline Si₃ N₄ contains a lower density of trapping centers, is more resistant to hot phosphoric acid etches and hydrofluoric acid etches than as-deposited LPCVD-Si₃ N₄, and is extremely effective as an O₂ -barrier film. The fact that crystalline Si₃ N₄ has a lower density of trapping centers lowers, and in some cases prevents altogether, the parasitic transistor caused by the as-deposited LPCVD-Si₃ N₄ film used in current STI technology. Furthermore, unlike the restrictive thicknesses that are specified in the current technology, this invention permits a larger range of crystalline Si₃ N₄ thicknesses (e.g., 5 nm to 10 nm) to be used as O₂ -barrier films in STI trenches. This allows a larger processing window for thickness controllability in manufacturing.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other objects, aspects and advantages will be better understood from the following detailed description of a preferred embodiment of the invention with reference to the drawings, in which:

FIGS. 1A, 1B and 1C illustrate the process of forming thin crystalline Si₃ N₄ films in STI structures; and

FIGS. 2A and 2B are, respectively, a bright-field transmission electron micrograph (TEM) of crystalline Si₃ N₄ and an electron diffraction pattern of the TEM.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT OF THE INVENTION

Referring now to the drawings, and more particularly to FIGS. 1A, 1B and 1C, there is shown the process of forming crystallized Si₃ N₄ films in STI trenches according to the invention. In FIG 1A, after a shallow trench has been etched, a thin thermal oxide (typically 10 nm thick) is grown to remove etch damage. Next, in FIG. 1B, a thin Si₃ N₄ film (5 to 10 nm) is deposited on top of the thermally-grown oxide layer in the STI trench. Then, in FIG. 1C, LPCVD-Si₃ N₄ is typically deposited at temperatures of 720° C. to 780° C., and as such, is generally deposited in an amorphous state. Immediately after deposition, a high temperature, rapid thermal anneal in pure nitrogen (RTN) or ammonia (NH₄) is conducted. Crystallization of LPCVD-Si₃ N₄ begins at 1050° C. and for anneal times on the order of 60 seconds. Temperatures greater than 1050° C. and/or anneal times greater than 60 seconds will induce further crystallization and grain growth of the LPCVD-Si₃ N₄ film. In addition, thicker LPCVD-Si₃ N₄ films (up to 10 nm) can be crystallized at temperatures less than 1100° C. This can be critically important in terms of limiting wafer warpage and slip line formation along wafer edges during the RTN process.

The typical morphology of crystalline Si₃ N₄ is shown in FIGS. 2A and 2B. FIGS. 2A and 2B are bright-field transmission electron micrograph (TEM) and corresponding electron diffraction pattern, respectively, of a 10 nm SiO₂ /4 nm Si₃ N₄ insulator-couple that has been annealed at 1100° C. At 1100° C., the Si₃ N₄ film is found to be largely crystalline. At 1050° C., the majority of the film is found to be amorphous; however, small crystallites of Si₃ N₄ are observed. Electron diffraction analysis of samples annealed at 1050° C. and 1050° C. shows that the crystalline S₃ N₄ film is the low-temperature, hexagonal (α) Si₃ N₄ phase.

Crystallized films of LPCVD-Si3N4 have much lower trap densities as compared to as-deposited LPCVD-Si₃ N₄ films. Results of C--V measurements of 10 nm SiO₂ /4 nm Si₃ N₄ insulator-couples which have been crystallized by high temperature RTN anneals (1050° C. to 1150° C.) show that the trap density, at a minimum, has decreased by an order of magnitude. In addition, crystallized LPCVD-Si₃ N₄ films show a heartier etch resistance to hot phosphoric acid and hydrofluoric acids. Etch rate studies show that crystallized LPCVD-Si₃ N₄ films have, at a minimum, a 45% lower etch rate in hot phosphoric acid than as-deposited Si₃ N₄ and as much as a 30% lower etch rate in pure hydrofluoric acid.

While the invention has been described in terms of a single preferred embodiment, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the appended claims. 

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is as follows:
 1. An improved shallow trench isolation (STI) structure for submicron integrated circuit devices comprising:a shallow trench of 0.5 μm or less etched in a silicon substrate; and a thin crystalline Si₃ N₄ liner 5 to 10 nm thick in said shallow trench.
 2. The improved STI structure recited in claim 1 further comprising a thin thermal oxide film of approximately 10 nm thickness grown in said shallow trench, said thin crystalline Si₃ N₄ liner being formed over the thin thermal oxide.
 3. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure comprising:a shallow trench of 0.5 μm or less etched in a silicon substrate; and, a converted Si₃ N₄ film 5 to 10 nm thick deposited by low-pressure chemical-vapor deposition (LPCVD) at a temperature between 720° C. to 780° C.
 4. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure as claimed in claim 3 wherein immediately after deposition of Si₃ N₄ film, a rapid thermal anneal is conducted between 1050° C. and 1150° C. for approximately 60 seconds therefore converting said Si₃ N₄ film from an amorphous state to a crystalline state.
 5. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure as claimed in claim 4 wherein said rapid thermal anneal is conducted at 1100° C. or less.
 6. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure as claimed in claim 4 wherein said rapid thermal anneal is conducted in pure nitrogen.
 7. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure as claimed in claim 4 wherein said rapid thermal anneal is conducted in ammonia.
 8. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure comprising:a shallow trench of 0.5 μm or less etched in a silicon substrate; a thermal oxide layer of approximately 10 nm thickness coating said shallow trench; and, a converted Si₃ N₄ film of 5 to 10 nm thickness deposited over said thermal oxide layer by low-pressure chemical-vapor deposition (LPCVD) at a temperature between 720° C. to 780° C.
 9. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure as claimed in claim 8 wherein said converted Si₃ N₄ film is formed by conducting a rapid thermal anneal between 1050° C. and 1150° C. immediately after deposition of Si₃ N₄ film, for approximately 60 seconds, therefore converting said Si₃ N₄ film from an amorphous state to a crystalline state.
 10. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure as claimed in claim 9 wherein said rapid thermal anneal is conducted at 1100° C. or less.
 11. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure as claimed in claim 9 wherein said rapid thermal anneal is conducted in pure nitrogen.
 12. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure as claimed in claim 9 wherein said rapid thermal anneal is conducted in ammonia.
 13. A crystalline silicone nitride (Si₃ N₄) film in a shallow trench isolation (STI) structure as claimed in claim 8 wherein said thermal oxide layer removes etch damage. 